Method of and apparatus for separating gas mixtures



June 23, 1942- E. F. YENDALL METHOD OF AND APPARATUS FOR SEPARATING GAS MIXTURES Filed Nov. 15, 1940 3 Sheets-Sheet l INVENTOR [bu A20 )ZAQAAL ATTORNEY June 23, 1942. "E. F; "Y'ENDALL METHOD OF AND APPARATUS FOR SEPARATING GAS MIXTURES 3 Sheets-Sheet 2 INVENTOR Filed NOV. 15, 1940 ATTORNEY June 23, 1942 E. F. YENDALL METHOD OF AND APPARATUS FOR SEPARATING GAS MIXTURES Filed Nov. 15, 1940 s Sheets-Sheet 3 INVENTO R EDWAAfi F Yes/0 444 ATTORNEY Patented a 23, 1942 carves eras s earner orries METHOD AND AIEPAEA'EHJS son dEP- ARATHNG GAS MEXTURE Edward F. Ycndall, Kenmore, N. Y assignor to The Linda Air Products @ompany, a corporation of @hio Application November 15, 194b, Serial No. middle 2% Claims. (Gl- 62-l'i:'i.5l

air on a relatively large scale by partial liquefac-- tion of the air and rectification at low temperatures, preferably in two stages. Such commercial oxygen preferably has a purity such that it contains no less than 99.6% oxygen, the permissible remainder being nitrogen and argon.

Atmospheric air and particularly the air near cities and industrial areas contains, besides rare gases and carbon dioxide, minute quantities of hydrocarbon gases such as methane, acetylene, ethane, propylene, and other combustible gases oi various kinds. Further traces of hydrocarbons may be introduced to the process airdue to the lubrication of the air'compressors used to compress the air to the relatively high pressures required for the liquefaction. Most of these minor impurities assume the liquid or solid state at liquid air and liquid oxygen temperatures and therefore will generally be carried by the liquefied portions of the air and by the liquid oxygen unless they are previously removed.

Since the nitrogen and argon content of commercial oxygen is not objectionable, such minute quantities of deleterious materials previously mentioned and including any carbon dioxide remaining in the air will be hereinafter referred to collectively as impurities. Only the very lightest hydrocarbons such as methane an ethylene have appreciable vapor pressures at the temperature of liquid oxygen; Hence, methane and ethylene ordinarily do not concentrate in appreciable quantities. Any carbon dioxide left in the compressed air will assume afinely-divided solid state and it not removed will pass into the rectifying apparatus and cause trouble by clogging narrow passages. Most of the carbon dioxide is customarily removed from the air by a preliminary treatment such as by passing the air through moist hydrated lime beds or by lines. Such residual carbon dioxide is therefore also objectionable and may be removed simultaneously with the hydrocarbon impurities. The

residual carbon dioxide will therefore be also included in the general term the impurities.

When gaseous oxygen is withdrawn from a rectifying apparatus adapted for the production of gaseous oxygen, many of the impurities will be concentrated at the place where the oxygen is vaporized. Such concentration oi hydrocar- V bon impurities in high purity oxygen may conwashing the air-with caustic solution. A small l.

amount of carbon dioxide, however, may remain and in time could cause trouble-in the separation apparatus particularly in liquid carrying stitute a serious hazard in the production equipment. When, however, liquid oxygen is produced by an apparatus suitable for producing oxygen in the liquid state, the impurities maypass out with the liquid withdrawn and, as is often the case, when the'liquid is subsequently vaporized for use, the hydrocarbon impurities will then be concentrated in the vaporizing apparatus where they would also constitute a hazard.

Efforts have been made to remove gaseous hydrocarbon impurities from the air before it is compressed by passing the air into intimate contact with an oil that has a high flash point. Such methods, however, do not completely remove the gaseous hydrocarbons and of course have no effect on any hydrocarbon introduced into the air due to the lubrication of the air compressors.- It has also been proposed to filter the air after compression but this 'merely is effective to remove entrained lubricants and does not remove impurities which are in the gaseous state at such portions of the manufacturing cycle. The hydrocarbon impurities existin raw air in very minute quantities which are of the thus cannot be filtered. In. order to avoid the hazard of accumulation of the hydrocarbon impurities, it has been proposed to continuously or periodically drain liquid from the oxygen vaporizer in order to limit the concentration to below a safe limit. Such method however may waste considerable oxygen, disturb the operation of the separation apparatus and does not entirely avoid the hazard of concentrating hydroture in the customary manner.

carbons in high purity liquid oxygen. In air separation plants which produce liquid oxygen, the impurities have been prevented from passing out with the liquid oxygen produced by eflecting a carefully conducted vaporization of all the liquid oxygen and recondensing the oxygen'vapors to produce the refined liquid oxygen product. Such method also does not entirely avoid the hazard of accumulating the hydrocarbons in high purity liquid oxygen.

It is a principal object of the present invention to provide an improved. method and apparatus for separating gas mixtures of relatively low boiling point into their constituents with the simultaneous elimination of impurities of relatively higher boiling point in a manner which overcomes the objections of the prior methods. th

er objects of this invention are to provide a method of and apparatus for separating air to produce nitrogen and oxygen including the simultaneous removal of impurities having a higher boiling point than oxygen; an improved procedure and apparatus for avoidingthe hazards caused by the presence of hydrocarbons in air during the separation of airby liquefaction and rectification; a method of and apparatus for effecting the concentration of hydrocarbon impurities in a liquid of relatively low oxygen content during the separation of air; apparatus for the removal of impurities that can be economically applied to existing air separation apparatus; a method of and apparatus for the safe elimination of impurities which maybe applied to existing procedures and plants for separating air without extensive alterations to such plants; a method of and apparatus for removing impurities before they reach the rectifying portions of an air separation apparatus; such a method and apparatus that may be particularly applied to air separationprocedures and apparatus adapted for efficiently producing liquid oxygen; and such method and apparatus the principles of which may also be effectively applied to air separation procedures and apparatus producing gaseous oxygen.

These and other objects and advantages of this invention will become apparent from the following description and the accompanying drawings,

carries substantially all the impurities. The gaseous fraction is then passed into the first stage of the rectification and the liquid fraction is almost completely vaporized at a relatively low temperature. The vapors resulting from such vaporization will be substantially free of the impurities and are therefore passed directly into the rectifying apparatus, preferably into the second stage portion. Substantially all the impurities will be retained in the vaporizer in a liquid which has a relatively low oxygen content and from the vaporizer the impurities are withdrawn from time to time as they accumulate. The compressed and cooled air may be partially expanded before or after the phase separation is eflected as will be specifically described hereinafter. The incoming air may also be supplied at a single pressure or at two pressures.

The vaporization 0i.the liquid phase portion may be eflected in several ways. For example, when it is desired to produce liquid oxygen, it is found desirable to vaporize the liquid phase portion by heat exchange with gaseous oxygen produced by the air separation apparatus, such heat exchange producing a liquid product of high purity. When it is desired to produce gaseous oxygen the vaporization of the liquid phase portion may be effected by heat exchange with portions of the incoming gaseous air to partly or completely condense such portions. The principles of the present invention may also be applied in certain apparatus forproducing gaseous oxygen in which the incoming air is cooled only to the condensation temperature and is not liq- .uefled. The incoming air in such case is scrubbed at an intermediate pressure with a portion of liquid air produced by condensingsome of the incoming air by effecting a heat exchange supplied with air cooled to its condensation temperature air.

According to the present invention, air which may be substantially freed of carbon dioxide by a preliminary treatment, is compressed, freed of moisture and cooled to a relatively low tempera- In most instances the air is sufficiently cooled so that a relatively small part of the air is liquefied. The cooled and partially liquefied air is then separated into liquid and gaseous portions or fractions in such a manner that the liquid fraction but containing relatively little liquid 'with portions of the condensed liquid air after it has been employed for the scrubbing of all the incoming air. Such heat exchange also efl'ects vaporization of the scrubbing liquid. the vapors of which are free from impurities and may be passed directly into the rectifying apparatus.

It is known that various forms of apparatus may be employed for preparing the incoming air and getting it into the condition desired for entry into an air separation rectifying column. In a two-stage air separating column the incoming air is introduced into the first stage preferably at a pressure of about. 75 lbs. per sq. in. gauge and at a temperature which corresponds to its condensing temperature at the pressure. When liquid oxygen is to be produced, the incoming air is sufilciently refrigerated so that a substantial portion thereof is liquefied, for example, in an air separation plant in which liquid oxygen is produced, the incoming air will contain about twenty percent liquid air whereas in an air separation plant producing gaseous oxygen the incoming air should have about three percent liquid.

The apparatus of Fig. 1 produces liquid oxygen. In this form of apparatus any of several known ways of preparing the air for rectification may be employed and a suitable specific apparatus is illustrated in which all the air, preferably after treatment to remove carbon dioxide, is compressed to a relatively high pressure in an air compressor indicated at l0. Such compressor may have three or four stages although for simplicity a single stage is indicated. The compressed air is conducted through a conduit ll into a heat exchanger I2, wherein it is countercurrently cooled by heat exchange'with a cold nitrogen product fiowing out through conduit If.

- 2,287,158 After leaving the heat exchanger l2, the compressed air is divided into two portions, one of which passes through branch conduit E to a heat exchanger It; in which a large portion is liquefied by heat exchange with the outflowing cold nitrogen leaving the separation apparatus through conduit ll. The cooled, and, partly liquefied portion of the air passesfrom the highpressure air tubes of heat exchanger it through The remaining portion of the compressed'airpasses through a branch conduit M to an expansion engine 22 which is coupled to a suitable means iorabsorbing power not shown in the interest of clearness of the drawing. The. expansion engine 22 expands the air it receives with the production of external work and consequently the production of a large volume of refrigeration so that the air discharged from the expansion engine through the conduit 23 is very cold. Such cold expanded air has substantially the same pressure as the first stage of rectification and is conducted directly into the lower mrtion of the scrubber-separator It. An gaseous portions of the entering air are thus thoroughly mixed and scrubbed with liquid portions of air in the bottom of the scrubber-separator is. If other forms of apparatus for refrigerating and partly liquefying the air are employed, all the air after refrigeration and reduction of pressure is introduced into the lower portion of the scrubber-separator it. Thus, the air might be compressed to a high pressure cooled and throttle expanded to the scrubber 29. The, condenser 29 is housed in a condenser housing 30 which holds a body of liquid oxygen rectified by the upper column. Above the condenser housing 30 is the second stage, low pressure or upper column 3! which is also filled with rectifying trays 28 similar to those in the lower column. Liquid air which contains about 30% oxygen accumulates in .the bottom or sump of the lower column 2'! and is transferred through a transfer line 32 into the upper column at an intermediate point thereof. Thelower column is also provided with a nitrogen shelf 33 for colpressure or the air may be compressed separately to two difierent pressures, one portion being compressed to relatively high pressure, cooled and expanded to scrubber pressure and the other portion compressed to a pressure only slightly higher than scrubber pressure, cooled and introduced into the scrubber together with the expanded high-pressure portion.

The scrubber-separator is preferably comprises a cylindrical tank which may have gas and liquid contact means interposed at an intermediate point therein such as a set of coarse screens 2%. The scrubber also may beprovided with suitable means for indicating the height of liquid air therein such as a gauge 25. The liquid should be maintained in the scrubber at a level. high enuogh for efiicient scrubbing action and such that there is a sufiicient space above the liquid in which entrained particles of liquid can separate and fall down so that no liquid will be carried off through theopening at the top of the scrubber. The opening at the top of the scrubber is connected with the lower portion of the air separation column shown generally at A, by a conduit 26. The gaseous fraction separated in the scrubber-separator i9 is substantially free of impurities and is thereforepassed directly into the air separation column.

The air separation column A is of a customary construction and comprises a lower column 21 containing rectifying trays or plates 28 and having at its upper end a condenser 29. The lower column 21 is thus in gaseous communication with r the insides of the tubes of condenser 29 whereby vapors rising in the column will be condensed by heat exchange with liquid oxygen which accumulates around the outside of the condenser tubes lecting a portion of the liquid rich in nitrogen which is condensed by the condenser 2%. Such nitrogen-rich liquid 'is transferred through a transfer line 3% to the upper end of the upper column to provide a reflux liquid for the upper column. Since the lower column is operated at approximately '75 lbs. per sq. in. pressure, the

transfer lines 32 and 34 are provided with expansion valves 35 and 36, respectively.

The nitrogen product is discharged from the upper end of the upper column 3i through a conduit 31 which, if desired, may connect directly with the conduit ii for conducting the nitrogen'directl-y to the heat exchanger it. However, as here shown, the nitrogen product is passed in heat exchanging relation with the liquid transferred through the nitrogen transfer line it by a heat exchanger 38 to which the conduits 31 and H are connected. The heat exchanger 38 serves to refrigerate the liquid transferred through the line 34 prior to its expansion through the valve 36 so that a greater proportion of the liquid will be available as reflux for the column.

The liquid portion of the incoming air which is collected in the lower part of the scrubberseparator It is transferred to a vaporizer 39 through a conduit to controlled by a valve ll. While any suitable form of apparatus for removing the higher boiling point impurities may be interposed in the conduit 60, in this form of apparatus it is preferable to vaporize the scrubber liquid by condensing gaseous oxygen. The vaporizer thus comprises a vaporizing chamber 39 surrounding a bundle of condenser tubes 62. The condenser tubes are provided with an upper header :32 which is connected with the gas space of the chamber 30 of the separating column by a conduit E3. The lower ends of the tubes 62 communicate with a lower header 4! which is provided with a liquid oxygen discharge conduit having two branches. One branch 45, controlled chamber 39. The liquid air that contains the concentration of impurities is withdrawn through a valved withdrawal connection 50 from'the bottom of the chamber 39. Sometimes it may be desirable to supply additional liquid to the J vaporizer 39 and this may be done by an auxiliary transfer line 5! which is connected between the vaporizer 39 and the lower portion of the lower column 21 and iscontrolled by a valve '52.

After the apparatus illustrated in Fig. 1 has been started and is in normal operation, the compressor ID will compress the preliminarily to form liquid oxygen which treated air to a pressure of about 2800 lbs. per sq. in. The moisture will be removed by suitable means such as traps and by refrigeration in the heat exchanger l2. The compressed air leaving the heat exchanger l2 through conduit l4 will be cooled to an intermediate low temperature, for example, a temperature that may be as low as about 40 C. The portion of the air that passes through conduit 2|, is expanded in the' expansion engine 22 with the production of external work to reduce the temperature of the expanded air leaving through conduit 23 to a temperature of about l65 C. The portion of the air passing through the conduit I5 is substantially liquefied in the liquefying heat exchanger IB and is expanded by passage through the expansion valve 20 to the pressure maintained in the scrubber-separator chamber which is substantially the same or only slightly higher than the pressure of the lower column 21. The gas and liquid portions are then intimately mingled inthe lower part of the scrubber-separator l9 whereby the gas portion of the entering air is thoroughly scrubbed, the perforated plates 24 assisting in the scrubbing action by breaking up large bubbles of gas. The gaseous fraction of the entering air separates from the liquid fraction in the upper part of the scrubber l9 and is passed directly into the lower column 21.

The vaporizer 39 operates under a pressure substantially thesame as the pressure existing in the upper column 3| of the air separation apparatus which is preferably a pressure only slightly above atmospheric pressure and sufiicient to drive the nitrogen out through the heat exchanger passages. passed through the conduit 40 into the vaporizer 39 is within, for example, about 5% of the amount which can be vaporized by the condensa tion of gaseous oxygen flowing through the conduit 43 to form the liquid oxygen produced. Minor adjustments in liquid quantities are made with valves 46, 49, 50, and 52 as explained below and the 5% variation would be affected by the amount of liquid drained from the connection 50.

The air which enters the lower column through the conduit 26 is at its condensation temperature corresponding to the pressure of the lower column which is about 75 lbs. per sq. in. gauge. Such air is liquefied by contact with cold liquefied portions of air which descend the column from the condenser 29. Thus; a rectifying action takes place in the column 21 so that air which is very rich in nitrogen reaches the condenser 29 and is liquefied'therein.

' Thus, the 5 liquid that reaches the bottom of the column 2! denser 42 and in the chamber 39 is'substantially the same. However, a temperature difference which causes eflicient heat exchange exists due to the difference in composition of the gas materials, thus the liquid air in the chamber 39 has a boiling point, due to its high nitrogen content, below the condensation point of oxygen at the same upper column pressure.

The operation of the apparatus is very easily balanced because if there should be slightly too much liquid in the chamber 39 for the oxygen being withdrawn to fully vaporize, the valve 46 may be opened sufliciently to increase the fiow of oxygen through the condenser tubes 42. This will provide more .heat and completely vaporize all the liquid being transferred into the chamber 39 except that which is to be withdrawn at 50. If, on the other hand, the amount of liquid being passed through the conduit 49 into the chamber 39 is slightly less than enough to cause condensation to liquid form of all the liquid oxygen being withdrawn, additional liquid may be supplied to The amount of liquid air reduction of efficiency of separation and a slightly the chamber 39 by opening the valve 52 so as to eflect a transfer of some of the liquid air collecting in the bottom of the column 21 to the chamber 39. The high boiling point impurities will accumulate in the chamber 39 and may be withdrawn together with some of the liquid air through the drain connection 50. Such drainage may be continuous at a relatively slow rate or may be preferably periodically done.

It will be seen that according to the invention the incoming air is separated into an impurityfree gaseous fraction'and an impurity-containing liquid fraction, the gaseous fraction is passed into the first stage of rectification, the impurities separated by the evaporation of the major part of the liquid fraction at a reduced pressure, and the evaporation effected by condensing a corresponding amount of gaseous oxygen product.

. The heat exchange which evaporates the liquid lower yield of oxygen from a given quantity of air compressed. The energy for operating the impurity-eliminating system thus results ultimately in increased power per unit of oxygen produced but this is offset by the elimination (ill supplies heat which causes the oxygen liquid collecting in the chamber 30 to boil and provides vapors for efiicient rectifying action in the upper column. Suflicient heat is also provided to evaporate all the oxygen being produced and such oxygen vapor passes through the conduit 43 to the condenser tubes 42 wherein it is condensed is withdrawn through conduit 44, conduit 41, and valve 43.

of hazards and particularly in the. double protection efiected by firstly, the removal of the major part'of the impurities at the drain 59 and secondly, the evaporation of the oxygen product in the chamber 30 and recondensation of the oxygen product in the condenser 42 which insures an impurity-free liquid-oxygen product.

In the form of apparatus illustrated in Fig. 2, the air separation column A is supplied with air at two pressures by separate compressors, and the scrubbed liquid is vaporized by condensing portions of the incoming air. The separating column is similar to that previously described and the similar parts have the same reference numerals. In this form of apparatus, only a portion of the air is compressed to a high'pressure in a high-pressure air compressor 55 and such high-pressure air is conducted through a countercurrent heat exchanger by a conduit 51. The high-pressure air then passes through a conduit 59 to the lower portion of the scrubberseparator 90. The scrubber-separator causes an intimate mixing of the liquid and gas portions of the high-pressure air with the aid of perfothrough to the upper portion of a scrubber column 64. The scrubber column 6d operates under a pressure only slightly above that of the lower column 2'5 and therefore a throttle valve 65 is interposed in the line 53. The liquid entering the scrubber M is substantially completely vaporized and is conducted from the top of the scrubber 64 through a conduit 6% to the lower part of the column 21.

A substantial portion of the air to be separated is compressed to a relatively low pressure in the compressor 61 and such compressed air is conducted through conduit as through the heat exchanger 56. The low-pressure air is then passed through an additional heat exchanger 58 and conducted by conduit 6% to the lower portion of the scrubber column 54, under the scrubbing trays 10 which are installed in the mid-portion of the column 66. The low-pressure air thus passes up through the trays it and is thoroughly scrubbed by the liquid introduced through conduit 53. The scrubbed air which is now free of impurities, flows out through conduit 66 to the lower column 21.. The gaseous fraction of the high-pressure air which is separated in the scrubber-separator 6e passes from the upper portion of the separator through a conduit ii to a heating coil lfiwithin the lower portion of the scrubber 65. The outlet of the heating coil l2 is connected to the lower portion of the column 21 by a conduit 53 which has interposed therein a throttle valve is.

In this embodiment of apparatus a gaseous oxygen product is withdrawn from the separating column A from the gas space of the chamber at through a conduit which conducts the oxygen to apassage it of the main countercurrent heat exchanger in order to recover refrigeration from the oxygen product. The nitrogen product passes from the top of the separating column through the conduit ll to the heat exchanger 58 and then by a connection ll to the cold end of the countercurrent heat exchanger 15%. The proportion of nitrogen passing through the heat exchanger 58 may-be regul'ihted by means of the valved connection it. The relatively high boiling point impurities which are washed down .and concentrated in the liquid that collects at the bottom portion of the scrubber be are withdrawn from the scrubber from time to time through the connection 78.

In the form of apparatus shown in Fig. 2 the operation of the separation column A is substantially unafiected by the scrubber arrangement. The compressor 55 compresses its portion of the air to a pressure of about 2000 lbs. per sq. in. Such high-pressure air is thus readily liquefied by the heat exchanger 58. The cooling of the high-pressure air however, should not be carried to such an extent that it is entirely liquefied becauseit is desirable that a separation of liquid and gas phases shall occur in the separator 80.

To insure the occurrence of vapor in the separator 60, the heat exchanger 58' is placed in the nitrogen conduit H to slightly superheat the nitrogen before it contacts the high-pressure air in exchanger 58. -An.expansion valve 59' is installed in the conduit 59 to allow operating the separatortfi at a pressure intermediate between the high pressure and the pressure of the lower column 21. The low-pressure air is compressed to a pressure only slightly above the pressure of the lower column 21, is countercurrently cooled in the heat exchangers 56 and 58 and is introduced into the scrubber 64 belowthe trays 10. The low-pressure air is thoroughly scrubbed in its passage through the trays 10 of the scrubber 64 and if the low-pressure air enters at a temperature slightly above its saturation temperature corresponding to the pressure of the 'lower column, some of the liquid air that enters through the conduit 63 will be vaporized and pass to the upper end of the scrubber 64. The portion of the high-pressure air that passes through the conduit 'H and through the heating coil 12 will heat the scrubber liquid that is collected in the bottom of the scrubber 65 in order to vaporize the same, and at the same time, the cooling produced by such vaporization will condense a large portion of the gas that enters the coil 12. Such heat exchange will occur because of the pressure difference between the gas in the coil 72 and the liquid in the scrubber 64. As the resulting liquid and gas is expanded through the valve it it is reduced to the pressure of the lower column 2?. Means for observing the liquid level in the scrubbers 60 and 6d are preferably provided. Such means, however, are not shown in the interest of clearness of the drawings.

The scrubber arrangement is readily balanced according to the level of the liquid in the scrubber column 64. If the liquid tends to rise too high, the valve It is closed slightly in order to increase the pressure in the coil I2 and thereby increasing the quantity of heat added to thevlower portion of the scrubber 65 so that more liquid is boiled oil. If it is desired to increase the liquid level in the scrubber 64, less heat is applied at the lower end thereof by opening the valve M and lowering the pressure and temperature difference between the gas in coil l2 and the liquid surrounding it.

In the form of apparatus of Fig. 2, the irreversible heat exchange is conducted at the expense of the pressure drop from the intermediate pressure of the scrubber 60 to the pressure of the column M and does not impair the eiiiciency and output of the rectifying apparatus A. The refrigeration lost in liquid Withdrawal at it is supplied by increased head pressure of the highpressure air or by supplying additional refrigeration to the compressed air.

Referring now to the form of apparatus for producing gaseous oxygen illustrated in Fig. 3,

the principles of the invention are applied to an oxygen separating system in which the compressed air, which may be supplied atone or two pressures, is cooled by counter-current heat ex.- changewith the products and by expansion to lower column pressure, to the saturation temperature corresponding to the pressure of the lower column 27, but in which there is substantially no liquid air contained in the incoming air. There is substantially no liquid iii the incoming air because sufficient refrigeration isremoved from the waste nitrogen leaving through conduit ll by the heat exchanger 38 and such refrigeration is thereby transferred to the upper column reflux and thus retained in the separation column A" and is not available in the main countercurrent heat exchanger to produce liquid. It is, therefore, necessary to insure the provision of a suflicient amount of liquid -for washing the .incoming air. All the incomingair which has been prepared as aforesaid, enters through conduit into the lower portion or a scrubber column at.

' of the upper column 3i.

At the upper end a: the scrubber column 8|,

v is provided a condenser 82 arranged so that the interior of its tubes are in communication with 1' the scrubber column 8|.

ber 88 surrounds the condenser 82. The upper liquid collecting shelf 84 which may be employed An evaporation champortion of the scrubber'8l is also provided with-a when desired to collect a portion of the liquid condensed by the condenser 82 for transfer through ,a conduit 8! controlled bya valve 88, to

- an intermediate point of the upper column 8| of the air separation apparatus A".' The scrubbe liquid collected in the lower part of the scrubber It is transferred to the evaporating chamber 88 by a transfer line 81 which is controlled by a valve 88. The vapors produced by the condenser vaporizer 82 collect in the chamber" and are passed into the rectifying column, preferably into an intermediate portion of theupper column 3| 1 by a conduit 89 which is controlled by a valve '89.

The impurities will collect in liquid in the lower part of the chamber 89 from which they may be withdrawn as desired through a withdrawal connection 98. The remaining gaseous portion of the incoming air which has been scrubbed free of impurities passes from the top of the condenser 82 through a conduit 9| into the lower part of the lower column 21.

At certain times, as when first starting up the apparatus, it may be desirable to transfer liquid into the vaporizer chamber 88 and for this purpose auxiliary transfer lines are employed, one line 92 connecting the lower end of the column 21 with the chamber 83. Altematively, liquid rich in nitrogen can be withdrawn from the shelf 33 through a conduit 93 which connects the shelf with the chamber 83. The

conduits 92 and 98 are controlled by valves 94,

will boil at'a pressure substantially equal to that The refrigeration caused by such vaporization will effect condensation of air within the condenser 82 to form liquid and such liquid will drop onto the scrubber trays in the scrubber 8|, thereby scrubbing the air which enters through the conduit 80. Such scrubber liquid flowing down the column 8i will wash down the impurities to the lower end of the column. The scrubber liquid containing the impurities will pass through the conduit 81 to the vaporizer 83 through a transfer valve 88 which reduces the pressure of the liquid to the pressure of the upper column. The gas produced in the vaporizer 83 will have a temperature substantially equal to the saturation temperature corresponding to the pressure of the upper column and may be directly passed into the upper column through the conduit 89 in order that the oxygen content thereof maybe washed there-- of the condenser is increased so that more liquid across the condenser 82.

It will be observed that in each form of apparatus illustrated the incoming compressed and cooled air is treated before it reaches the recti-' fying column, that the incoming air. is divided into a liquid, and gaseous fraction in a manner that insures the retention of the impurities in the liquid phase, that the liquid in which the I impurities are concentrated has a relatively low oxygen content, that the liquid phase in which the impurities are concentrated constitutes 'a small portion of the entire input air, that the larger gas phase portion of the air is passed directly into the first stage rectification or lower column, that the liquid phase fraction containing the impurities is vaporized in a manner that separates and concentrates the impurities at a place where they can be readily removed and that the vapors produced by vaporizing such liquid fraction are passed to the rectifying stages for rectification. In the preferred embodiment of. this invention as applied to an apparatus producing liquid oxygen, the vaporization of the liquid fraction is eflected by heat exchange with a gaseous oxygen separation product to form the desired liquid oxygen product and although there results a slight reduction of rectification emciency, an impurity-free liquid oxygen product is assured.

It will be evidentthat certain features of this invention maybe used independently of others and that changes in steps of the method and features of the apparatus may be made without departing from the essentials of the invention. For example, the impurity-removal system may also be applied to systems for the separation of other gas mixtures than air and which also contain higher boiling impurities. It-ls also contemplated that the principles of the invention may be employed for removing substantially all the carbon dioxide of the air.

I claim:

1. In a process for the separation of air by rectiflcation in two stages at low temperatures, the

steps of cooling and partly liquefying the enter- 7 cation -in two stages at low temperatures, the

steps which comprise cooling and partially liquefying the entering air; separating the liquid phase portion of such cooled air from the vapor phase portion; passing the vapor phase portion directly into the higher pressure first stage of rectification; separately vaporizing the liquid phase portion to concentrate said impurities therein; removing the impurity containing concentrates; and passing the vapors of such vaporization into the second stage of rectification.

3. Process according to claim 2 in whichthe vaporization of said liquid phase portion is effected by h at exchange with gaseous oxygen produced by the rectification to substantially liquefy such oxygen product.

4. In a process for the separation of air containing impurities by rectification in two stages at low temperatures the steps of cooling and partially liquefying the entering air, scrubbing such cooled and partially liquefied air with its liquid fraction to retain the impurities in such liquid fraction; separating the liquid fraction from the gas phase fraction; scrubbing another portion of incoming air at a lower pressure with such liquid fraction; condensing the gaseous fraction of said first scrubbing by effecting heat exchange with said scrubbing liquid to substantially completely vaporize said scrubbing liquid; removing the imurity containing concentrate and passing all the gas resulting from said second scrubbing and the liquid produced by said condensation to said rectifying stages.

5.In a process for the separation of air containing impurities by rectification in two stages at low temperatures, the steps of cooling and partially liquefying the entering air; scrubbing the cooled air with a liquid fraction produced by condensing a portion of such cooled air; passing the scrubbed gaseous air directly to the first stage rectification; vaporizing substantially completely the scrubbing liquid by heat exchange with gaseous portions of the enteringair to effect such condensation; removing an impurity containing remainder of such vaporization and passing the vaporized scrubbing liquid to said rectifying stages. I

6. A process for separating air by rectification in two stages according to claim in which said vapors produced by vaporization of said scrubber liquid are passed into the second stage of rectification.

'7. A process for separating air by low temperature rectification according to claim 5 in which a portion of the air which is recondensed to form scrubbing liquid is withdrawn before it is used for scrubbing incoming air, expanded and passed into the second stage rectification.

8. .A process of eliminating higher boiling impurities in the separation of a gas mixture by rectification at low temperatures which comprises cooling such gas mixture containingim purities to partly liquefy said gas mixture; separating the liquid phase portion of such cooledmixture from the gas phase portion in a manner such that'said impurities are retained in the liquid portion; vaporizing a major part of said liquid portion to concentrate said impurities in the remainder; withdrawing said remainder; and subjecting said gas phase portion and the impurity-free vapors produced by the vaporization of said liquid phase portion to rectification to separate the components of said gas mixture in the substantial absence of said impurities.

9. A process according to claim 8 in which the vaporization of said liquid portion is effected by heat exchange with a gaseous product of the separation to liquefy such product.

10. A process of eliminating higher boiling impurities in the separation of a gas mixture by rectification at low temperatures which comprises cooling such gas mixture containing impurities to substantially a condensation temperature; liquefying a portion of said gas mixture; scrubbing the cold gaseous portions of said mixture with. said liquefied portion to retain said impurities in said liquid portion; vaporizing a major portion of said liquid containing the impurities to concentrate said impurities in. a relatively small remainder of liquid; withdrawing said remainder; and subjecting the scrubbed gaseous portions of said mixture and the vapors of the vaporization of said liquid to rectification to separate the components of said gas mixture.

11. Process according to claim 10 in which the portion of the mixture liquefied is condensed by a heat exchange effecting the vaporization of said liquid containing the impurities.

12. Apparatus for eliminating higher boiling impurities prior to the separation of a gas mix- I ture by rectification at low temperatures which comprises means for separating the liquid phase fraction of a cooled and partly liquefied gas mixture from the gaseous fraction thereof in a manner such that said impurities are substantially entirely contained in said liquid fraction; means for vaporizing a major part of said liquid fraction to concentrate the impurities in the remainder; means for withdrawing such remainder; and means for subjecting said gaseous fraction and the vapors of said vaporization of the liquid fraction to rectification.

13. Apparatus for eliminating higher boiling impurities prior to the separation of a gas mixture by rectification according to claim 12 in which said means for vaporizing said liquid fraction comprises a condenser arranged for condensing a gaseous product of the separation. w

14. Apparatus for eliminating higher boiling impurities prior to the separation of a gas mixture by rectification according to claim 12 in which said means for vaporizing said liquid fraction comprises a condenser arranged for condensing a portion of said cooled gas mixture.

15. Apparatus for eliminating higher boiling impurities prior to the low temperature rectification of air which comprises means for cooling the air to be separated to condensation temperature and liquefying a portion of such air; means for scrubbing the uncondensed portionof the cooled air with the liquefied portion of the air and, sepa rating the uncondensed portion from the liquid portion whereby said liquid carries said impurities; a rectifying apparatus; means for passing said uncondensed portion of air into said rectifying apparatus; means for vaporizing a major part of said liquid portion to separate said impurities;

means for withdrawing said impurities and means for passing the vapors from said vaporizing means into said rectifying apparatus.

16. Apparatus for eliminating higher boiling impurities prior to the low temperature rectifica- 55.

tionof air according to claim 15 in which said vaporizing means comprises a condenser arranged to receive and liquefy an oxygen product of said rectification.

17. Apparatus for eliminating higher boiling impurities prior to the low temperature rectification of air according to claim 15 in which said tion of air which comprises means for cooling the I air to be separated to condensation temperature vaporizing means comprises a device arranged for efiecting heat exchange between said liquid portion and portions of saiduncondensed air before passage into said rectifying apparatus. v

18. Apparatus for eliminating higher boilin impurities prior to the low temperature rectificaand liquefying a portion of such air; means for scrubbing the uncondensed portion of the cooled air with the liquefied portion of the air and separating the uncondensed portion from the liquid portion whereby said liquid carries said impurities; a two-stage rectifying apparatus having a lower and an upper column; means for passing said uncondensed portion of the air from said scrubbing and separating means into the lower column of said apparatus; a condenser having an evaporator chamber; means for passing liquid from said scrubbing and separating means into said evaporator chamber; means for passing-vapors from said evaporator chamber into said up per column; means for passing an oxygen product from said rectifying apparatus to said condenser; means for'withdrawing a liquefied oxygen product from said condenser; and means for withdrawing gas-1,158

column; means for passing portion of air from said scrubbing and separating a concentrate of said impurities from said evapora'tor chamber.

19. Apparatus for eliminating higher boiling impurities prior to the low temperature rectification of air, according to claim 18 in which said means for passing liquid from said scrubbing and separating means to said evaporator chamber is provided with a valve for controlling the flow and reducing the pressure of said liquid substantially to that of said upper column. I

20. Apparatus for eliminating higher boiling impurities prior to the low temperature rectification of air according to claim 18, which includes means for returning liquid from said condenser to said rectifying apparatus at a controlled rate; and means for transferring desired amounts of liquid from said lower column to said evaporator chamber.

21. Apparatus for eliminating higher boiling impurities prior to the low temperature rectificae means into heat exchanging relation with the liquid in the lower portion of said scrubber column and thereafter into said rectifying apparatus; said heat exchange evaporating a maior part of the liquid; means for withdrawing a concentrate of said impurities from the lower portion of said scrubber column and means for passing gaseous air substantially free from impurities from the upper portion of said scrubber column into said rectifying apparatus.

22. Apparatus for eliminating higher boiling impurities prior to the low temperature rectification of air which comprises means for cooling the air to be separated to condensation temperature; a two-stage rectifying apparatus having upper and lower columns; and an impurityseparating device comprising a lower chamber having gas and liquid contact means therein, a

liquid collecting space below said contact means and a condenser above said contact means; an evaporator chamber surrounding said condenser;

' meansfor admitting cold compressed air into tion of air which comprises means for cooling the I air to be separated to condensation temperature and liquefying a portion of such air; means for scrubbing the uncondensed portion ofthe cooled air with the liquefied portion of the air and separating the uncondensed portion from the liquid portion whereby said liquid carries said impurities; a rectifying apparatus; a scrubber column having upper and lower portions and scrubbing means therebetween; means for passing said liquid portion from said scrubbing and separating means to said scrubber column above 'said' scrubbing means; means for passing another portion of cold air at a lower pressure into said scrubber column below said scrubbing means whereby said low pressure portion of air is scrubbed by said liquid portion and said liquid portion carrying the impurities of all the air collects in the lower portion of said scrubber tion of air according to claim 22including means for controllably transferring portions of liquid from said lower column to said evaporator chamber.

24. Apparatus for eliminating higher boiling impurities prior to the low temperature rectification of air according to claim 22including means in said lower chamber of the separating device for collecting a portion of the liquid condensed bysaid condenser and means for transferring said collected portion of liquid to said upper column.

- EDWARD F. YENDALL.

saiduncondensed 

